Process for the single-bath dyeing of cellulose and polyamide fiber blends according to the pad dyeing technique

ABSTRACT

Process for the single-bath dyeing of blends of cellulose fibers and synthetic polyamide fibers with reactive dyestuffs and nonreactive metal complex dyestuffs according to a continuous or semi-continuous method of the pad dyeing technique, by applying to these fibrous materials aqueous padding liquors which contain alkaline agents in addition to combinations of the abovementioned dyestuffs, and then, optionally after intermediate drying, submitting the material so treated in the alkaline medium to the action of heat or allowing it to dwell at room temperature or at slightly elevated temperature for the fixation of the dyestuffs.

United States'Patent 1191 von der Eltz et al.

14 1 Mar. 5, 1974 1 PROCESS FOR THE SINGLE-BATH DYEllNG OECELLULOSE ANDPOLYAMIDE FIBER BLENDS ACCORDING TO THE PAD DYEING TECHNIQUE [7 5Inventors: Hans-Ulrich von der Eltz,

' Frankfurt/Main; Hans-Peter Maier,

Sulzbach/Taunus; Dietfried Suchy, Fulda, all of Germany [73] Assignee:Farbwerke Hoechst Aktiengesellschaft Vormals Meister Lucius & Bruning,Frankfurt/ Main, Germany 22 Filed: Feb. 23, 1972 21 Appl. No.: 228,756

[30]- Foreign Application Priority Data Feb. 25, 1971 Germany 2108875[52] US. Cl. 8/21 B, 8/26 [511 Int. Cl D06p 3/82 [58] Field of Search8/21 B, 25, 21 A, 163, 26

15 6] References Cited UNITED STATES PATENTS 7/1963 Casty 8/163 X3,252,963 5/1966 Blackhall ct al. 260/147 3,293,238 12/1966 Chang260/153 FOREIGN PATENTS OR APPLICATIONS 1,155,148 6/1969 Great Britain8/21 B 652,584 8/1964 Belgium 8/21 8 Primary ExaminerHerbert B. GuynnAssistant Examiner-Bruce H. Hess Attorney, Agent, or FirmCurtis, Morris& Safford [5 7 ABSTRACT Process for the single-bath dyeing of blends ofcellu- 8 Claims, N0 Drawings nique PROCESS FOR THE SINGLE-BATH DYEHNG ECELLULOSE AND POLYAMHDE FIBER BLENDS ACCORDING TO THE PAD DYEINGTECHNIQUE The present invention relates to a process for the single-bathdyeing of cellulose and polyamide fiber blends according to a continuousor semi-continuous method of the pad-dyeing technique.

It is known that textile materials of cellulose fibers can be dyed withreactive dyestuffs by reacting them with the hydroxyl groups of thecellulose fibers under alkaline conditions. Pad-dyeing methods are ofparticular importance in this field because they'can be carried out infully or semi-continuous manner. For the fixation of the above dyestuffson cellulose fabrics, an important and economic dyeing technique isrepresented by the pad-batch process at which dyestuff and alkali areapplied together to the fiber and fixation of the woundup dyeing ensuesat room temperature within a certain dwelling time [cf. SVF-Fachorgan16, (1961), pages 320340]. In the dyeing of blended fabrics of celluloseand polyamide fibers this application method. could only be employed, upto now, for the cellulose fiber portion of the textile material, inwhich case dyeing of the polyamide fiber component had to be effected bycross-dyeing, subsequent to the after-treatment of the reactive dyeing,in discontinuous manner with acid, metal complex or disperse dyestuffsfrom an acid or neutral medium at the boiling temperature or at anelevated temperature. This two-bath dyeing method has the drawback thatit is very complicated and allows no continuous working. The sameapplies when working according to the pad drying process.

However, blended fabrics of native or regenerated cellulose fibers andsynthetic polyamide fibers can be dyed or printed continuously accordingto the thermosol process with disperse and reactive dyestuffs. Accordingto this single-bath dyeing technique an aqueous composition whichcontains in addition to disperse and reactive dyestuffs also alkali aswell as, optionally, further additives such as cross-linking andthickening agents, is applied to the textile material, then the fabricis dried and submitted to a heat treatment at about 175 220C for 30 to60 seconds. By the thermosol operation, the polyamide fiber portion ofthe blended fabric is fixed and is, thus, imparted its optimumtechnological properties. At the same time, the disperse dyestuff isfixed on the polyamide fiber and the reactive dyestuff on the cellulosefiber. This process, however, is very expensive because of the dyestuffsused; the fastness properties, especially those as to wet processing ofthe dyeings are not satisfactory in many cases.

Now, it has been found that the above-cited difficulties and drawbackscan be overcome and that blends of cellulose fibers and syntheticpolyamide fibers can be dyed with reactive dyestuffs and non-reactivemetal complex dyestuffs according to a fully or semicontinuoussingle-bath method of the pad-dyeing techwhen applying to these fibrousmaterials aqueous padding liquors which contain alkaline agents besidescombinations of the above-mentioned dyestuffs, and then optionally afterintermediate drying, exposing the material thus treated in the alkalinemedium to the action of heat or allowing it to dwell at room temperatureor at slightly elevated temperature for the fixation of the dyestuffs.

This process allows combinations of one or several reactive dyestuffsand of one or several metal complex dyestuffs to be simultaneously fixedon the fiber blends,

the reactive dyestuff substantially dyeing the cellulose 5 fiber portionof the material and the metal complex dyestuff and, as the case may be,further proportions of the reactive dyestuff, dyeing the polymidecomponent. This result could not be foreseen by those skilled in the artand it is, thus, extraordinarily surprising that metal complex dyestuffscan be fixed on the polyamide material in water-soluble or dispersedform by a heattreatment, especially under alkaline conditions. Such aresult was the more surprising as the specialist knows that the disperseor acid dyestuffs usually employed for dyeing polyamide fibers are moreor less destroyed at the elevated temperatures of the thermosol processunder alkaline conditions and that reproducible and level dyeings cannotbe obtained for this reason. According to the invention it could not beexpected that metal complex dyestuffs may be fixed on polyamidesespecially from an alkaline medium by dwelling at room temperature sincethe pad dwell process generally does not allow to obtain reproducibleand level dyeings with the dyestuffs otherwise suitable for polyamidefibers, especially with acid and disperse dyestuffs, at roomtemperature.

According to this invention the textile material is impregnated on apadding machine at C to C with an aqueous padding liquor containing thedissolved reactive dyestuff, the dissolved or dispersed metal com.-

plex dyestuff, alkaline substances and, optionally, further auxiliaryadditives, and then freed from the excess liquid.

For the fixation of the dyestuff mixtures applied in this manner bywhich the fixing operation is carried out under the action of heat,there are available different methods:

Thus, for example, the fibrous material can be submitted in moist state,immediately after having been 40 padded with the dyestuff preparation,to a steam process of from 30 to 180 seconds, preferably from 30 toseconds, at a temperature within the range of from to 108C, preferablyof from 103 to 105C. (onebath pad wet-steam process). Along anotherprocedure, the pad-dyeings can also be steamed, after an intermediatedrying step at relatively low temperatures up to C, for 5 to 15 minutes,preferably for 7 to 10 minutes, at a temperature from 100 to 108C,preferably at from 100 to 105C (one-bath pad-steam process), or they canbe thermosoled on a tenter frame or a sieve drum drier by forcingthrough the goods dry hot air by suction or by contact heating attemperatures within the range of from 190 to 220C within from 10 to 60seconds, preferably for 60 seconds at 195C (heat fixation process).intermediate drying after the padding process may, however, be omittedif, by treating the padded material for example, on the hot-flue, for 1to 6 minutes, preferably for 90 to seconds, at temperatures within therange of from 170C, preferably at about C, together with the drying ofthe goods, fixation of the dyestuff is effected (one-bath pad dryingprocess). The various possibilities of a heat fixation described aboveaccording to the present invention offer, simultaneously with the singlebath processing, above all the special advantage of a continuousoperation technique. The large tolerance with regard to the fixationtemperature and/or fixation time is balanced according to the claimedprocess by variation of the alkali concentration. By means of theseoperating methods very high speeds of the goods can be obtained.Furthermore, the results of the dyeing can be reproduced to a highdegree.

The favourable conditions offered by the single-bath dyeing method aremaintained when the blended fabrics padded simultaneously with thedyestuff combinations and with alkali are rolled onto a beam and thefibrous material is allowed to dwell in moist state at room temperatureor at slightly elevated temperature within the range of from to 60C for2 to 24 hours, preferably for 8 to l4'hours (one-bath'pad-batch processor short-time pad-batch process). This semi-continuous dyeing techniqueis characterized by a high degree of utility because of the energy-savedand expensive aggregates for intermediate drying and fixing are notnecessary.

After dyeing, the material is rinsed, soaped and finished in usualmanner. When pursuing the working conditions described above, the metalcomplex dyestuff causes no or only little soiling of the celluloseportion. For the dyeing with the reactive dyestuffs it is important thatduring the washing process the aqueous baths are not neutralized withacetic acid, since otherwise part of the reactive dyestuff is fixed onthe polyamide fiber portion of the material which causes a change inshade.

The process of the invention for dyeing textile materials which consistof cellulose and polyamide fiber blends has the advantage, in comparisonwith the single-bath dyeing technique generally used for this purpose,that considerably improved fastness properties can be obtained,especially with respect to wet processing. For example, the fastness toperspiration of the dyeings was given the mark 5, a result which couldnot be obtained by other. methods, especially by the singlebath dyeingtechnique mentioned as prior art. The twobath processes for dyeing thesaid fiber blends are surpassedby the novel process in that the workingmeth ods are simplified and the costs are reduced.

In the process of the invention, preferably such reactive dyestuffs areused which contain, as the reactive component, at least one vinylsulfonegroup or at least one group capable of fonning the vinylsulfone groupunder the action of the alkaline agents during the dyeing process. Inthis case, it is not important whether the said radicals are bound tothe dyestuff molecule directly or via a bridge member, especially NH orNR- (R lower alkyl). Among the groupings which can be converted into thereactive vinylsulfone group by alkaline substances, there may bementioned, for example, the B-sulfatoethyl-sulfone group, the,8-thiosulfatoethyl-sulfone group, the fi-phosphatoethyl-sulfone group,the B-chloroethyl-sulfone group, the B-dialkylaminoethyl-sulfone groupas well as the corresponding sulfonylamino groups, especially theethyionylamino radical. All the otherknown reactive dyestuffs,especially those which contain, as the reactive group, at least oneB-(2,2,3,3-tetrafluorocyclobutyl)- acrylaminoor B-( 2,2,3,3-tetrafluoro-4-alkylcyclobutyl)-acrylamino group can be used for thenovel dyeing method. As parent substances for these dyestuffs there areespecially suitable those of the anthra quinone, azo and phthalocyaninedyestuff series, in which case the azo and phthalocyanine dyestuffs maybe metal-free or metallized.

As non-reactive metal complex dyestuffs there are used in the process ofthis invention 1:2-chromium or cobalt complex compound of azo dyestuffs,especially monoazo dyestuffs, i.e. compounds in which 2 molecules of oneazo dyestuff or 1 molecule each of two azo dyestuffs different from oneanother are bound to a chromium or cobalt atom in complex-bound form.The complex may contain, for example, one disazo dyestuff and onemonoazo dyestuff or, preferably, two identical or different monoazodyestuff molecules. F urthermore, there may be used water-soluble, metallized azo dyestuffs which contain per dyestuff molecule only onemetal atom in complex bound form lzl-metal complex compounds),especially copper, and also chromium or cobalt. These azo dyestuffscontain as groups forming the metal complex linkage preferablyo,o-dihydroxy azo groupings.

According to the above process, there may be used in the paddingliquors, on principle, all inorganic substances having an alkalineeffect, such as sodium carbonate, sodium bicarbonate, trisodiumphosphate, disodium phosphate, sodium hydroxide, sodium silicates, thecorresponding potassium compounds or mixtures of these alkalis inamounts of from 3 to 30 g, preferably from 5 to 20 g, per liter ofpadding liq'uor, said alkali content depending, on the one hand, on thedyestuff amounts used and, on the other hand, on the efficiency of theenergy supplied for fixation. The pH-value of the dyebath generally iswithin the range of from 8 to 13.

Depending on the type of the fixation method, the padding liquors mayadvantageously contain electrolytes, especially crystallized sodiumsulfate or purified sodium chloride in amounts ranging from 10 to 40 g,preferably of about 30 g, per liter of padding liquor.

Commercial wetting and thickening agents may also be added to thedyebaths used, a capillary-active mixture containing branched aliphaticcarboxylic acid esters, optionally partially saponified phosphoric acidesters of aliphatic alcohols of medium molecular weight, small amountsof fatty acids or soaps and as wetting agent known higher oxalkylates ofaliphatic or aliphatic-aromatic' sulfonic acids being .especiallyrecommended, since it advantageously influences the intensity andlevelness of shade. Similar good effects with regard to the colour yieldand the levelness are provided by alkali metal salts of them-nitro-benzenesulfonic acid and the polyalkylene glycols, preferablypolyethylene glycols, having an average molecular weight of about 400 to800. The above-mentioned auxiliaries are used in amounts within therange of from 5 to 20 g/l, preferably 10 to 15 g/l of the dyeingpreparation.

The textile material to be dyed in accordance with the invention whichconsists of blends of native or regenerated cellulose fiber andsynthetic polyamides in a ratio of from 50 50 to 15 has the workingstage of a flat-surface textile structure, for example a woven orknitted fabric.

The following Examples serve to illustrate the invention, the parts andpercentages being by weight, unless otherwise stated.

EXAMPLE 1 16 g of the reactive dyestuff of formula were dissolved in thetwo to four fold amount of hot water and this solution was cooled toabout 50C by adding about the same amount of cold water. Another aqueousdyestuff solution prepared in the same manner by using 8 g of thelz2-chromiurn complex compound of the dyestuff of formula l0 g ofm-nitrobenzenesulfonic acid (sodium salt) and 10 g of crystallizedsodium sulfate, was poured into the solution of the reactive dyestuffand the mixture was Furthermore, g of sodium bicarbonate were added tothe dyebath thus prepared.

With this padding liquor, a blended fabric of cotton and syntheticpolyamide fibers in the ratio of 60 z 40 was impregnated at to C on apadding machine and freed from the excess liquid by squeezing, then itwas submitted to intermediate drying at to C on a hot-flue andsubsequently steamed at 100 to C for 7 to 10 minutes. Then, the fabricthus dyed was rinsed with neutral, cold water and then with hot water ofabout 80C and soaped at room temperature for 5 minutes with a solutioncontaining 1 g of a condensation product of oleic acid andN-methyl-taurine (as sodium salt) per liter of water.

After rinsing with hot and cold water and drying had been repeated, 21dyeing was obtained in which the cotton fiber portion of the materialwas dyed in orange shade and the polyamide fiber component in dark blueshade.

The following Table 1 indicates further dyestuff combinations which maybe used for the dyeing of blended fabrics of cellulose and polyamidefibers according to the method described in Example 1, the dyestuffamounts to be used in each case and the shades obtainmade up to a volumeof 1 liter by adding cold water. 25 able on the fiber blend components:

TABLE 1 7 Amount,

Example Dyestuff combination grams Shade 2 .t SOaH 15 Cotton fiber:brilliant yellow.

l s 03H 1:2-chromium complex compound.

19 Polyamide fiber: navy blue.

17 Cotton fiber: intense yellow.

S OaNa TABLE 1-Continuo l Amount, Exzunpln lJyr-stull' combination gramsShade LHI ll .TOzNu l3 l'olyzimllln lilmr: blue. 7, Nnois -N' N i 1l-chromlum complex compound.

4 [S O H1 11 Cotton fiber: turquoise blue.

CuPc

S O2-NH -SO2CH2CH2OS 03H (CuPc=copper phthalooyanine).

S O2-NH2 12 Polyamide fiber: red.

N=NfiC-CH3 HOC N CH 1:2-chromium complex compound.

EXAMPLE OH OH 16 g of the reactive dyestufi of the formula OCH;

I'lOaS-O-CHPCHr-S O 2- mamas 2 g of m-nitrobenzenesulfonic acid (sodiumsalt) and g of crystallized sodium sulfate, was poured into the solutionof the reactive dyestuff and the mixture was made up to a volume of 1liter by adding cold water. Furthermore, 16 cc. of sodium hydroxidesolution of 38Be were added to the dyebath thus prepared.

With this padding liquor; a blended fabric of cotton and syntheticpolyamide fibers in the ratio of 60 was impregnated at 20 to 25C on apadding machine and freed from the excess liquid by squeezing and thensteamed without intermediate drying at 103 to 105C for seconds.Subsequently, the fabric thus dyed was rinsed in the same way asdescribed in Example l, aftertreated and finished. A dyeing was obtainedin which the cotton fiber portion of the material was dyed ingolden-yellow shade and the polyamide fiber component in bordo shade.

Further dyestuff combinations suitable for the dyeing of blended fabricsof cellulose and polyamide fibers as indicated in Example 5, thedyestuff amounts to be used in each case and the shades obtainable onthe components of the fiber blend in these cases are indicated in thefollowing Table 2:

TABLE 2 Example Dyestufi combination Amount,

grams Shade S OaH 17 Cotton fiber: orange.

TABLE Z-Cominued Amount, Example Dycstufi combination grams Shade OH HO9 Polyamide fiber: dark blue.

l I -N=N H5CSO2 INTI- I S 0 z 7 l 1: 2chromlum complex compound. 7 13Cotton fiber: turquoise.

s 0311 2-3 CuPc S O2NH- S O2CH2CH2O- S 03H 11-2 (CuPc=copperphthalocyanlne). S Oz-NH: 13 Polyamide fiber: red.

1; 2-chromium complex compound.

8 $03K 10 Cotton fiber: yellow.

N=N(HI -CH?--C H H 0-0 N I N s 03H OZCIIZ CIIQO"-SO3TI S OrlNa F I) N;-N-C-CC1Ia J n o-N N l 0 O H \N/ 1:2-chromium complex compound.

l SOT-N H-CH;

l :Zz-mball, complex compound.

12 Iolyamidc fiber: navy blue.

EXAMPLE 9 and from 16g of the 1:2-cobalt complex compound of 8 g of thereactive dyestuff of the formula the dyestuff of the formula CH3 Ha i NN I NSQ2-em-cH,--0-soarr /NSzQ-N=NE(u3-Cm k/ fSQaH H3O H HO- /N 8 g ofthe lz2-cobalt compound of the dyestuff of formula SOPNHZ N C C in thesame manner as described in Example 9, the ad- Hoditives indicatedtherein were added and it was made 11 up to a dyebath volume of 1 literby adding water.

' With the padding liquor so prepared, a cotton/polyamide blended fabricin the ratio of 50 50 was dyed in the same manner as described inExample 9, and, upon the aftertreatment, a dyeing was obtained in whichthe 1 cotton fiber portion of the material was dyed in navy and 1 l g ofthe 1:2-chromium complex compound of blue shade and the polyamidecomponent in red violet the dyestuffs of formula shade.

OH HO C1 EXAMPLE 1 1 mega O 16 g of the reactive dyestuff of the formula01 l I N=N- w K 7 son; 7

l were dissolved in the two to four fold amount of hot Y 1 water andthis solution was cooled to about 50C by adding cold water. Anotheraqueous dyestuff solution o 40 prepared in the same manner using 10 g ofthe 1:2- were flooded with about 200 cc. of boiling water and cobaltcomplex compound of the dyestuff of formula dissolved while stirringthoroughly. After having added 500 cc. of cold water 10 g ofm-nitrobenzensulfonic acid (sodium salt), 10 g of crystallized sodiumsulfate and 20 g of calcined sodium carbonate were stirred in thissolution whereupon the dyebath so prepared was & made up to a volume of1 liter by adding cold water.

With this padding liquor, a blended fabric of cotton and syntheticpolyamide fibers (ratio 50) was impregnated at 20 to 25C, freed from theexcess liquid 50 by squeezing and then dried at 140C for 90 to 120 sec-(31 onds on a hotflue. Subsequently, the material thus treated wasrinsed in the way indicated in Example 1, soaped with a non-ionicdetergent and finished. A dye-' and 20 g of a polyethylene glycol havingan average ing was obtained in which the cotton component of themolecular weight of about 400, was poured into the sofiber blend wasdyed in scarlet red shade and the polylution of the reactive dyestutTand the mixture was amide fiber component in dark blue shade. made up toa bath volume of 1 liter by adding cold water. Furthermore, 10 g ofsodium bicarbonate were EXAMPLE added to the dyebath so prepared.

An aqueous solution was prepared from 35 g of the With this paddingliquor, ablended fabric of equal reactive dyestuff of the formulaproportions of cotton and of synthetic polyamide fibers was impregnatedat to C on the padding machine and squeezed, then dried at 110C andtherrnosoled at 190C for to seconds by means of hot air on a tenterframe. Subsequently, the fabric thus dyed was rinsed with neutral, coldwater and then with hot water at about C and soaped at room temperaturefor 5 minutes with a solution containing 1 g of the condensation productof oleic acid and N-methyl tau rine (as sodium salt) per liter of water.After rinsing and drying had been repeated a dyeing was obtained 10TABLE 3 Example Dyestufi combination OH HCI) 1:2'cobalt complexcompound.

no NH:

llOaS- 1:2cobalt complex compound.

1:2'chrornium complex compound.

NH-C O-GH:

OCu-O Amount,

grams Shade 17 Cellulose fiber: yellow.

l S 0 H 16 Polyamide fiber: red.

26 Cellulose fiber: navy blue.

$SO II 12 Iolyamide fiber: brown.

15 Cellulose fiber: blue.

13 Polyamide fiber: bordo.

TABLE 3 Continued Example I) ycstufi' combination Amount,

grams Shade 15. S 0 H I110 1 2-cobalt complex compound.

1:2-cobalt complex compound.

H 0 Cl 0 H 1:2chr0mi11m complex com pound.

1:2-c0balt complex compound.

11 Cellulose fiber: orange.

4 Polyamide fiber: anthracite.

8 Cellulose fiber: yellow.

Polyamlde fiber: anthracite.

Dyestufl combination 1:2-chromium complex compound.

Exam tile EXAMPLE l7 15 g of the reactive dyestuff of the formula SOiNawere dissolved in the two to four fold amount of hot water and thissolution was cooled to about 50C by adding cold water. Another aqueousdyestufi solution prepared in the same manner using 17 g of the 1:2-chromium complex compound of the dyestuffs of formula HO C1 I i lAmount,

grams Shade HO Cl 13 was poured into the solution of the reactivedyestuff and the mixture was made up to a volume of 1 liter by addingcold water. Furthermore, 5 g of a capillaryactive mixture containingesters of branched fatty acids having from six to 12 carbon atoms and oflow molecular secondary alkanols, phosphoric acid esters of alkanolshaving from four to 8 carbon atoms, small amounts of fatty acids havingfrom 12 to 18 carbon atoms or the salts thereof and alkansulfonic acidshaving from 10 to 20 carbon atoms, 16 cc. of sodium hydroxide solutionof 38Be and 30 g of crystallized sodium sulfate were added to thedyebath so prepared.

With this padding liquor, a blended fabric of equal proportions ofcotton and of synthetic polyamide fibers was impregnated at 20 to 25C ona padding machine, squeezed and then rolled up in moist state. Toprotect the padded material from irregular drying the rolled up textilematerial was enveloped in a plastic sheet and was allowed to dwell inthis state at room temperature for 12 hours for dyestuff fixation. Then,the fabric thus dyed was first thoroughly rinsed with neutral cold waterand then with hot water at C and soaped for 5 minutes at the boilingpoint with a solution containing per liter of water 1 g of thecondensation product of oleic acid and N-methyltaurine (as sodium salt).After rinsing with hot and cold water had been repeated a dyeing wasobtained in which the cotton fiber component was dyed in yellow shadeand the polyamide fiber component in blue shade.

The following Table 4 indicates further dyestuff combinations suitablefor dyeing cellulose and polyamide fiber blends in a manner described inExample 17, this summary also containing the dyestuff amounts to be usedin each case and the shades obtainable on the blended fabric:

TABLE 4 Amount, Example Dyestufi combination grams Shade 18 S OzNa 15Cellulose fiber: yellow.

' o1- N=NfiC-CH:

( 3 0 O H H 0-0 N 1:2-chr0mium complex compound.

12 Polyamide fiber: blue.

TABLE 4-Continued Amount, Example Dyestufi combination grams Shade 15! tr r t 13 Cellulose fiber; turquoise blue.

' [SO -NIL- -S() -CIl Cll' -OS H] :7 1-2 (In l'o I i 03 ira((lulc=eoppur phtlialooyanino).

S (J -Nll l2 lolyamirle fiber; dark orange. Z -N N(J(JCll ll ll )II II()(J N 1 :Q-chromium complex compound.

v 21 Cellulose fiber: turquoise blue.

- S OzNH S O2:CH2CHz-OS 03H z NiPc [SOaH]:

(NiPc=niekel phthalocyanine).

(3 H I110 O H H0 15 Polyamide fiber: black.

NZM W N=N l i (Jl lzl-ehromium eomplex compound (mixed chroming). 21 rro v r ro 1s Cellulose fiber: bordo.

N=N y (\JHa /{NS 02CH2CHz-0S 03K 1 S 03K I S 03K O -NH; 7 Polyamidefiber: red violet.

OH HOC\ /N 1:2eobalt complex compound.

We claim:

1. A process for the single-bath dyeing of a fibrous blend of cellulosefibers and synthetic polyamide fibers with a reactive dyestuff and anon-reactive metal complex dyestuff in a continuous orsemi-continuousprocedure of the pad-dyeing technique which comprises applying to afibrous blend of cellulose fibers and polyamide fibers an aqueousalkaline padding liquor containing a reactive dyestuff for saidcellulose fibers and a non-reactive metal complex dyestuff for saidpolyamide fibers, padding the fibrous blend thus treated with saidpadding liquor, and then fixing said reactive dyestuff on said cellulosefibers and said non-reactive metal complex dyestuff on said polyamidefibers by al lowing said fibrous blend to dwell between 2 and 24 hoursin moist condition at about room temperature or at slightly elevatedtemperature.

2. A process according to claim 1 wherein said fibrous blend is wound-upand allowed to dwell at about room temperature.

3. A process according to claim 1 wherein said fibrous blend is wound-upand allowed to dwell at a temperature of about to about C 4. A processaccording to claim 1 wherein said aqueous alkaline padding liquorcontains, as a capillaryactive mixture, a branched-chain aliphaticcarboxylic ous alkaline padding liquor contains a polyalkylene glycol ofaverage molecular weight of about 400 to about 800 as an auxiliaryagent.

7. A process according to claim 1 wherein said reactive dyestuff has avinylsulfone group or a group which forms a vinylsulfone group inalkaline medium.

8. A process according to claim 5 wherein said dwell is between 8 and 14hours.

2. A process according to claim 1 wherein said fibrous blend is wound-upand allowed to dwell at about room temperature.
 3. A process accordingto claim 1 wherein said fibrous blend is wound-up and allowed to dwellat a temperature of about 30* to about 60*C.
 4. A process according toclaim 1 wherein said aqueous alkaline padding liquor contains, as acapillary-active mixture, a branched-chain aliphatic carboxylic acidester, a partially saponified phosphoric acid ester of an aliphaticalcohol of medium molecular weight, a fatty acid or soap, and a higheroxalkylate of an aliphatic or an aliphatic-aromatic sulfonic acidwetting agent.
 5. A process according to claim 1 wherein said aqueousalkaline padding liquor contains an alkali metal salt of m-nitrobenzenesulfonic acid as an auxiliary agent.
 6. A process according to claim 1wherein said aqueous alkaline padding liquor contains a polyalkyleneglycol of average molecular weight of about 400 to about 800 as anauxiliary agent.
 7. A process according to claim 1 wherein said reactivedyestuff has a vinylsulfone group or a group which forms a vinylsulfonegroup in alkaline medium.
 8. A process according to claim 1 wherein saiddwell is between 8 and 14 hours.